Hydrothermal apparatus for synthesizing crystalline powders

ABSTRACT

Berlinite crystalline powder of uniform particle size and high purity is prepared by repeated thermal cycling to react a mixture of aluminum hydroxide or aluminum oxide and an excess of concentrated phosphoric acid in a sealed pressure vessel. The vessel is preferably held in a horizontal orientation and rotated about a longitudinal axis during the reaction. The product powder is useful in growing large single crystals that have surface acoustic wave applications. Crystalline powder of alpha-gallium orthophosphate may be prepared using the same apparatus and a similar procedure.

CROSS REFERENCE TO PRIOR APPLICATIONS

This application is a continuation-in-part of Ser. No. 315,778, filed Oct. 28, 1981, abandoned, which in turn is a division of Ser. No. 230,077, filed Jan. 30, 1981, now U.S. Pat. No. 4,324,773, issued Apr. 13, 1982.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to an apparatus for preparing crystalline powders of alpha-aluminum orthophosphate and alpha-gallium orthophosphate.

2. Description of the Prior Art

Alpha-aluminum orthophosphate (berlinite) and alpha-gallium orthophosphate (GaPO₄) are among several alpha-quartz isomorphs that have for decades been synthesized for research purposes. An attempt to grow large single crystals of berlinite began after World War II, in an effort to find new piezoelectric crystals for frequency control applications. The project ended a few years later, because success was achieved in quartz crystal growth and because quartz was considered superior for the piezoelectric devices known then. Specifically, it was concluded that berlinite had a lower Q and lower coupling coefficient than quartz. Furthermore, tests on both X and Y cuts of berlinite plates, showing a negative frequence drift with increasing temperature, indicated that there was little chance of finding a zero temperature cut similar to the AT cut of quartz.

Interest in berlinite was renewed in 1976, when Barsch and Chang found that berlinite does have temperature-compensated cuts and that the coupling coefficient for surface acoustic wave (SAW) devices can be four times greater than for quartz.

Several processes for preparing berlinite have been reported in the technical literature (A. F. Huttenlocker, Z. Krist. 90, 508 (1935); W. Jahn et al., Chem. Erde 16, 75 (1953); and E. D. Kolb et al., J. Crystal Growth 43, 313 (1978)). Three processes for preparing GaPO₄ were described by Perloff (J. Amer. Cer. Soc. 39, 83 (1956)).

Recently, Drafall and Belt, of the Rome Air Development Center, described procedures for seeded hydrothermal growth of single crystals of berlinite for SAW applications. (RADC-TR-80-73, Final Technical Report, March, 1980). Among the three approaches to nutrient preparation described in their report, the best results were achieved by reacting Al(OH)₃ with excess H₃ PO₄ according to the reaction:

    Al(OH).sub.3 +H.sub.3 PO.sub.4 →AlPO.sub.4 +3H.sub.2 O

The amount of acid was adjusted so that the final solution was 6M in H3PO₄. The reactants were heated in a sealed silver-lined autoclave under a gradient of 20°-30° C., with temperature increasing from 120°-250° C. at a fixed rate of about 5° C./day. Euhedral crystals in the 1-4 mm range were produced.

SUMMARY OF THE INVENTION

In accordance with the present invention, an apparatus is provided for preparing powders of alpha-aluminum orthophosphate or alpha-gallium orthophosphate. The apparatus comprises, in combination, a vessel comprising a substantiallly cylindrical tubular element having a shrinkable and reusable fluoropolymer lining that is initially longer than the tubular element, means for supporting the vessel with its cylinder axis in a substantially horizontal orientation, means for rotating the vessel about its cylinder axis, means for controlling temperatures in the vessel, and means for compensating for shrinkage in the fluoropolymer liner, the compensating means comprising a sealing plug and a removable annular ring at one end of the vessel that sealingly support the liner, while permitting the liner to thermally expand and contract at the seal.

In operation, the present invention provides a process for preparing crystalline powders of alpha-aluminum orthophosphate or alpha-gallium orthophosphate. The process comprises the steps of:

(a) heating a sealed pressure vessel containing a mixture comprising a compound selected from the group consisting of aluminum hydroxide, aluminum oxide, and gallium sesquioxide and an excess of concentrated phosphoric acid to a first temperature between about 180° C. and about 235° C.,

(b) cooling the vessel to a second temperature between about 125° C. and about 150° C.,

(c) repeating steps (a) and (b) at least one more time,

(d) rapidly cooling the vessel from the first temperature to near ambient temperature, and

(e) recovering the resultant crystalline powder. Preferably, the pressure vessel is held in a horizontal position and rotated about a longitudinal axis during the reaction.

The present invention provides several advantages over the prior art. The apparatus is simpler, lighter, easier to use, and less expensive to build than that of the prior art. The resultant high-purity powder, consisting of uniform size, crystalline grains, is useful as nutrient material in the growth of single crystals of alpha-quartz isomorphs for SAW device applications.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a sectional view of an apparatus of the present invention before the fluoropolymer liner has shrunk.

FIG. 2 shows a sectional view of an apparatus of the present invention after the fluoropolymer liner has shrunk.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides an apparatus for preparing crystalline powders that are isomorphs of alpha-quartz. The apparatus includes a substantially cylindrical pressure vessel supported with its long dimension in a horizontal orientation, means for rotating the vessel about a longitudinal axis, and means for controlling temperatures in the vessel.

The pressure vessel, or autoclave, has a fluoropolymer lining to inhibit acid corrosion of the walls. Any fluoropolymer that can withstand the conditions of temperature and pressure in the corrosive environment of the autoclave without softening substantially is suitable as a liner material. Among these, poly(tetrafluoroethylene) and PFA (copolymer of perfluorinated ethylene and perfluorinated alkylvinylether) are particularly suitable; chlorotrifluoroethylene and polyvinylidene fluoride are not, because they soften at the high temperature. In principle, the fluoropolymer could be sprayed on the autoclave walls; in practice, however, sprayed coatings contained micropores that permitted autoclave wall corrosion.

The autoclave also includes means for compensating for shrinkage of the fluoropolymer liner. It is characteristic of the fluoropolymers used as liners in the present apparatus that they shrink with repeated cycling between ambient and elevated temperatures. To compensate for this relaxation-shrinkage, the liner is initially longer than the tubular element that forms the body of the autoclave. At one end of the autoclave, therefore, the liner initially extends beyond the end of the tubular element. The liner extension is sealed on its inner surface by a plug, which preferably has at least one, more preferably two, O-rings to accomplish the sealing, while permitting the liner to thermally expand and contract. An annular extender ring forms a snug fit to the outer surface of the extention and provides mechanical support for the liner. Ultimately, i.e., after several cycles between ambient and elevated temperatures and pressures, the liner will have shrunk (typically, about 3-5%) to fit the autoclave body and obviate the need for the annular extender ring. It is desirable to use extender rings of decreasing length in successive powder preparation runs.

Conventional autoclaves, fabricated from high-strength materials, are suitable. A Morey-type autoclave is convenient to use and is adequate to tolerate the required pressures (˜50 000 kPa). If an autoclave having a demountable seal at one end is used, the fluoropolymer lining may be machined from a solid cylinder. A tubular autoclave, having demountable seals at each end, is preferred for two reasons. First, it permits the fluoropolymer liner to be fabricated from extruded tubular stock, without machining. In addition, it makes loading and unloading of material from the autoclave, as well as cleaning the autoclave, simpler. Since the force required to seal the ends of the autoclave at a given pressure is essentially proportional to the cross-sectional area of the cylinder, a small cross section is advantageous. However, the cross section is preferably large enough to accommodate the desired volume of reactants without causing the collapsing strength of the liner to be exceeded during cooling. Autoclave dimensions, while not critical, involve a compromise among these competing factors.

The autoclave is supported with its cylinder axis horizontal to promote uniform distribution of the material. The support includes means for rotating the autoclave to promote uniform temperature and growth (without clumping) and to reduce the tendency for material to adhere to the liner. The rotation rate is not critical. The range from about 5 to 60 rpm is suitable, with 10 to 30 rpm preferred. If the rate is too low, the purposes of rotation, discussed above, are not achieved; if too high, there is a tendency for the tumbling of the particles against one another to have an undesirable grinding effect.

Surrounding the autoclave is a cylindrical furnace for heating the autoclave to above 235° C. The exterior temperature of the autoclave is monitored in a conventional manner, for example using thermocouples. Although not measured directly, the interior temperature is believed to be generally within about 5° C. of the measured temperature during heating and cooling cycles, closer at the temperature extremes. Interior temperatures are uniform to within about ±1° C.

In one embodiment, preparing powders of berlinite by the process of the present invention comprises first mixing chemical grade aluminum hydroxide fine powder with an excess of concentrated phosphoric acid. Electronic grade 85% H₃ PO₄ is commercially available and is suitable. Heating the mixture in an autoclave then causes the following reaction to take place:

    Al(OH).sub.3 +H.sub.3 PO.sub.4 →AlPO.sub.4 +3H.sub.2 O.

Alternatively, chemical grade aluminum oxide (Al₂ O₃) powder may be used in place of Al(OH)₃, to cause the reaction:

    Al.sub.2 O.sub.3 +2H.sub.3 PO.sub.4 →2AlPO.sub.4 +3H.sub.2 O

An advantage of using Al₂ O₃ is that the berlinite yield is greater for a given autoclave volume, since only half as much water is generated. A disadvantage is the sluggish reaction rate. Furthermore, the reaction does not go to completion if the Al₂ O₃ powder is too coarse (maximum particle size >1 μm). Just a very small quantity of Al₂ O₃ (<0.1% of the original amount) remaining in the system can cause serious problems in subsequent single crystal growth. If the required fine powder were available at a reasonable cost, the Al₂ O₃ process would be preferred.

The reactions require that the vessel temperature be at least about 125° C.; otherwise, the product is AlPO₄.2H₂ O. As the reaction proceeds, the temperature is cycled, preferably between about 130° and 200° C. Berlinite shows retrograde solubility. Thus, at temperatures above about 235° C., its solubility is so low that very little material precipitates.

Preferably, a temperature cycle is completed in less than about seven days, more preferably in about one day. Of course, the first cycle, beginning at ambient temperature, takes longer than later cycles. If the rate of temperature increase is too high, there is excessive nucleation of particles, and the desirably coarse grains do not result.

The amounts of reactant are chosen to meet two goals. The first is to yield a liquid product whose acid molarity is between 5 and 8, 7.3 being particularly suitable. A ratio of about 1.5-2 mL of 85% H₃ PO₄ per g of Al(OH)₃ generally yields such a product; 1.8 mL/g is preferred. If Al₂ O₃ is used instead of Al(OH)₃, about 2.0-2.5 mL/g is suitable, with about 2.3 preferred.

The second goal is to maximize the yield of crystalline powder in a limited autoclave volume. If too much of the autoclave volume (i.e. >90%) is filled by the reactants, a single (liquid) phase fills the entire volume at 200° C. and excessive pressures may develop. Within this volume constraint, in a preferred procedure, a quantity of fine crystalline berlinite (<100 mesh), the residue (after sieving) of previous syntheses, is also added to the system as seeding material. The amount of fine berlinite is a determining factor of the number of particles in the product.

Preferably, the autoclave is held with its long dimension substantially horizontal and more preferably it is also rotated about a longitudinal axis as the reaction takes place. The horizontal position provides a uniform temperature; and rotation provides agitation, which increases the reaction rate, reduces undesirable coagulation, and yields a product in loose powder form having uniform grain size. Rotation also contributes to uniform temperature in the autoclave.

Although the reaction is complete within about two days, particle size at that time is undesirably small. To produce coarser grains, the temperature is cycled repeatedly. Small grains go into solution preferentially as the temperature is reduced, and crystallites grow as the temperature is increased. Typically, the particles grow to an acceptable size in about three weeks. Because of berlinite's retrograde solubility, the reaction mass must be cooled rapidly and removed from the system to avoid dissolution of the berlinite product into the acid after the desired particle size has been achieved. To accomplish this, the autoclave is removed from the furnace and sprayed with water. Cooling to near room temperature takes about 10 to 15 minutes. More rapid cooling, while possible, would increase the stress on the liner and thus reduce its lifetime. After being cooled, the solution is filtered and the crystalline berlinite powder is washed, dried, and sieved. Particles of size less than 100 mesh are used as seeding material in later syntheses. The coarse granular berlinite powder is used in growth of single crystals. No material is wasted.

For subsequent growth of large single crystals, optimum particle size is in the range from about 20-100 mesh, with 20-50 mesh preferred (all mesh sizes quoted herein are U.S. sieve). Smaller particles tend to go into suspension, which is deleterious to the growth of large single crystals; larger particles go into solution too slowly. A narrow particle size distribution is desirable, because it provides a uniform dissolution rate and thus permits nearly all the nutrient to be used during the single crystal growth operation. For this reason, particles of size >10 mesh are less desirable; however, since the present process generally yields no particles that large, there is no problem. By the present process, a greater fraction of the product powder has particle size in the preferred range than is achieved by prior art processes. For example, a typical reaction yields 40 percent of the crystalline berlinite granules greater than 50 mesh, 50 percent between 50-90 mesh, and 10 percent less than 90 mesh.

Starting with chemical grade Al(OH)₃ and electronic grade H₃ PO₄, emission spectroscopic analysis of the crystalline powder product shows the following impurities: Si:20 ppm, B:20 ppm, Ga:70 ppm, transition metals: <100 ppm, alkaline earths: <30 ppm, and alkalies: <20 ppm.

Similar to the process and apparatus described above for preparing berlinite are those for preparing GaPO₄. The latter merely involves substituting high purity (99.99%) Ga₂ O₃ for Al(OH)₃ or Al₂ O₃ and preferably cycling the temperature between about 140° C. and about 225° C., instead of the lower temperatures used in berlinite preparation. The reaction involving gallium is:

    Ga.sub.2 O.sub.3 +2H.sub.3 PO.sub.4 →2GaPO.sub.4 +3H.sub.2 O

FIG. 1 depicts a sectional view of an apparatus of the present invention. The pressure vessel comprises a tubular element 10 having flanges 11 at each end for securing two demountable caps 12. The vessel is protected from corrosion by fluoropolymer liner 13, cap liner 14, and sealing plug 21. As shown in FIG. 1, liner 13 extends beyond tubular element 10 at one end, and the extension is supported by extender ring 22. Two O-rings form the seal between plug 21 and liner 13 and permit liner 13 to expand and contract with temperature changes. Optionally, an O-ring may also be placed between fluoropolymer elements 13 and 14 to ensure sealing, particularly when a vessel of large cross section is used. The vessel is attached at one end to a demountable coupling 15 that permits the vessel to be rotated about an axial shaft 16 driven by a motor (not shown). Preferably, coupling 15 is thermally insulating to avoid heating the motor by conduction along shaft 16. At its opposite end, the vessel is attached to a shaft 17, supported in a bearing (not shown). The vessel is enclosed in split furnace 18, with split pipe 19 filling the gap that results from the flanges. A thermocouple (not shown) fitted into a hole 20 in the pipe measures the temperature. A conventional plunger seal, or other seal not requiring the flanged structure, would obviate the need for the split pipe.

FIG. 2 depicts the apparatus of FIG. 1 after liner 13 has shrunk to its final length and extender ring 22, no longer needed, has been removed.

The following examples are presented in order to provide a more complete understanding of the invention. The specific techniques, conditions, materials, and reported data set forth to illustrate the principles and practice of the invention are exemplary and should not be constructed as limiting the scope of the invention.

EXAMPLE 1

A 3.2 L autoclave oriented with its cylinder axis horizontal was loaded with a mixture of 1300 g Al(OH)₃, 2.3 L of concentrated (85 wt. %) H₃ PO₄, and 300 g AlPO₄ (size <100 mesh). The temperature of the autoclave was cycled between 130° C. and 200° C. for three weeks while the autoclave was rotated about its axis at 20 rpm. The temperature cycle period was one day. The reaction yielded 1.8 kg of berlinite having the following particle size distribution:

20-45 mesh--283 g (15.8%)

45-60 mesh--868 g (48.6%)

60-70 mesh--232 g (13.1%)

70-100 mesh--250 g (14.1%)

<100 mesh--151 g (8.45%)

EXAMPLE 2

The autoclave of Example 1 was loaded with 1200 g Al₂ O₃ and 2.7 L of 85 wt. % H₃ PO₄ (no AlPO₄ was added). The autoclave temperature was cycled daily between 140° C. and 185° C., while the autoclave was rotated about its axis at 20 rpm. After 25 days, 2.1 kg of berlinite had been produced having the following particle size distribution:

20-45 mesh--106 g (5.0%)

45-100 mesh--1860 g (87.1%)

<100 mesh--168 g (7.9%)

EXAMPLE 3

The autoclave of Example 1 was loaded with a mixture of 960 g Ga₂ O₃, 2.5 L of 85 wt. % H₃ PO₄, and 880 g α-GaPO₄ (size <90 mesh). The autoclave temperature was cycled between 150° C. and 210° C. for 30 days while the autoclave was rotated about its axis at 10 rpm. The temperature cycle period was one day. The reaction yielded 2080 g of α-GaPO₄ having the following particle size distribution:

20-50 mesh--345 g (16.6%)

50-90 mesh--1285 g (16.6%)

<90 mesh--453 g (21.8%) 

We claim:
 1. An apparatus for preparing crystalline powders of alpha-aluminum orthophosphate or alpha-gallium orthophosphate comprising in combination(a) a pressure vessel comprising a substantially cylindrical tubular element having a shrinkable and reusable fluoropolymer lining that is initially longer than the tubular element, (b) means for supporting the vessel with its cylinder axis in a substantially horizontal orientation, (c) means for rotating the vessel about its cylinder axis, (d) means for controlling temperatures in the vessel, and (e) means for compensating for shrinkage in the flouropolymer liner, the compensating means comprising a sealing plug and a removable annular ring at one end of the vessel that sealingly support the liner, while permitting the liner to thermally expand and contract at the seal.
 2. The apparatus of claim 1 in which the vessel comprises a tubular member having demountable seals at each end.
 3. The apparatus of claim 1 in which the fluoropolymer is poly(tetrafluoroethylene). 